[go: up one dir, main page]

WO2016044688A1 - Addition de boue contenant des minéraux pour la formation d'un agent de soutènement - Google Patents

Addition de boue contenant des minéraux pour la formation d'un agent de soutènement Download PDF

Info

Publication number
WO2016044688A1
WO2016044688A1 PCT/US2015/050855 US2015050855W WO2016044688A1 WO 2016044688 A1 WO2016044688 A1 WO 2016044688A1 US 2015050855 W US2015050855 W US 2015050855W WO 2016044688 A1 WO2016044688 A1 WO 2016044688A1
Authority
WO
WIPO (PCT)
Prior art keywords
proppant
slurry
equal
recycled
ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2015/050855
Other languages
English (en)
Inventor
Mark Windebank
Johan LORICOURT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imerys Oilfield Minerals Inc
Original Assignee
Imerys Oilfield Minerals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imerys Oilfield Minerals Inc filed Critical Imerys Oilfield Minerals Inc
Priority to US15/512,087 priority Critical patent/US20170275209A1/en
Publication of WO2016044688A1 publication Critical patent/WO2016044688A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/62625Wet mixtures
    • C04B35/6263Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00Clay-wares
    • C04B33/02Preparing or treating the raw materials individually or as batches
    • C04B33/04Clay; Kaolin
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62204Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/62695Granulation or pelletising
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/80Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/80Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • C09K8/805Coated proppants
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232Titanium oxides or titanates, e.g. rutile or anatase
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/528Spheres
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5296Constituents or additives characterised by their shapes with a defined aspect ratio, e.g. indicating sphericity
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C04B2235/727Phosphorus or phosphorus compound content

Definitions

  • the present disclosure relates to methods of making and using proppants for fractured earth having a high compressive strength combined with good conductivity. It also relates to methods of making and using anti-flowback additives for use in fracturing operations.
  • subterranean structure if is possible to bore into the earth and set up a well where oil and natural gas are pumped out of the deposit.
  • These wells are large, costly structures that are typically fixed at one location.
  • a well may initially be very productive, with the oil and natural gas being pumpabie with relative ease.
  • the oil or natural gas near the well bore is removed from the deposit, other oil and natural gas may flow to the area near the well bore so that it may be pumped as well.
  • the more remote oil and natural gas may have difficulty flowing to the well bore, thereby reducing the productivity of the well.
  • a propping agent also known as a proppant in the fracturing fluid.
  • the goal is to be able to remove as much of the injection fluid as possible while leaving the proppant behind to keep the fractures open.
  • the term "proppant” refers to any non-liquid material that is present in a proppant pack and provides structural support in a propped fracture.
  • Anti-flowback additive refers to any material that is present in a proppant pack and reduces the flowback of proppant particles but still allows for production of oil at sufficient rates.
  • the terms "proppant” and “anti-flowback additive” are not necessarily mutually exclusive, so a single particle type may meet both definitions. For example, a particle may provide structural support in a fracture and it may also be shaped to have anti-flowback properties, allowing it to meet both
  • proppants For example, for use in deep wells or wells whose formation forces are high, proppants must be capable of withstanding high compressive forces, often greater than 10,000 pounds per square inch (“psi"). Proppants able to withstand these forces (e.g., up to and greater than 10,000 psi) are referred to as high strength proppants. If forces in a fracture are too high for a given proppant. the proppant will crush and collapse, and then no longer have a sufficient permeability to allow the proper flow of oil or natural gas. Other applications, such as for use in shallower wells, do not demand the same strength proppant, allowing intermediate strength proppants to suffice. These intermediate strength proppants are typically used where the compressive forces are between 5,000 and 10,000 psi. Still other proppants can be used for applications where the
  • the shape of the proppant has a significant impact on how it packs with other proppant particles and the surrounding area.
  • the shape of the proppant can significantly alter the permeability and conductivity of a proppant pack in a fracture.
  • Different shapes of the same material offer different strengths and resistance to closure stress. It is desirable to engineer the shape of the proppant to provide high strength and a packing tendency that will increase the flow of oil or natural gas. The optimum shape may differ for different depths, closure stresses, geologies of the surrounding earth, and materials to be extracted.
  • Another property thai impacts a proppant's utility is how quickly it settles both in the injection fluid and once it is in the fracture.
  • a proppant that quickly settles may not reach the desired propping location in the fracture, resulting in a low Seve! of proppants in the desired fracture locations, such as high or deep enough in the fracture to maximize the presence of the proppant in the pay zone (i.e., the zone in which oii or natural gas f!ows back to the well). This can cause reduced efficacy of the fracturing operation.
  • a proppant disperses equally throughout all portions of the fracture. Gravity works against this ideal, pulling particles toward the bottom of the fracture.
  • proppants with properly engineered densities and shapes may settle more slowly, thereby increasing the functional propped area of the fracture. How quickly a proppant settles is determined in large part by its specific gravity. Engineering the specific gravity of the proppant for various applications is desirable because an optimized specific gravity allows a proppant user to better place the proppant within the fracture.
  • Still another property to consider for a proppant is its surface texture.
  • a surface texture that enhances, or at least does not inhibit, the conductivity of the oil or gas through the fractures is desirable. Smoother surfaces offer certain advantages over rough surfaces, such as reduced tool wear and a better conductivity, but porous surfaces may still be desirable for some applications where a reduced density may be useful.
  • All of these properties, some of which can at times conflict with each other, must be weighed in determining the right proppant for a particular situation.
  • Bauxite is a natural mineral comprising various amounts of four primary oxides: alumina (A! 2 0 3 , typically from about 80% to about 90% by weight), silica (Si0 2 , typically from about 1 % to about 12% by weight), iron oxide (Fe 2 0 3i typically from about 1 % to about 15% by weight), and titania (Ti0 2 , typically from about 1 % to about 5% by weight).
  • alumina A! 2 0 3 , typically from about 80% to about 90% by weight
  • silica Si0 2 , typically from about 1 % to about 12% by weight
  • iron oxide Fe 2 0 3i typically from about 1 % to about 15% by weight
  • titania titanium oxide
  • bauxite is known to have a higher toughness but a lower hardness than technical grade alumina-based ceramics.
  • bauxite Since toughness is a primary mechanical characteristic to consider in improving the crush resistance or compressive strength of ceramics, bauxite is of interest for use in proppants.
  • the microstructure of bauxite is characterized primarily by three phases: 1 ) a matrix of fine alumina crystal; 2) a titania phase where titania is complexed with alumina to form aluminum titanate (AI 2 Ti0 5 ); and 3) a mullite phase ⁇ 3Ai 2 0 3! 2Si0 2 ).
  • a partial substitution of aluminum by iron atoms is possible.
  • bauxite with lower levels of silica and iron oxide are preferred.
  • proppants and anti-flowback additives that have an excellent conductivity and permeability even under extreme conditions. It may also be desirable to provide an improved manufacturing process to improve the efficiency by which proppants and anti- flowback additives are made. It may also be desirable to improve the efficiency of manufacturing proppants and anti-flowback additives while improving the mechanical properties of the proppants and anti-flowback additives. It may also be desirable to provide proppants and anti-flowback additives that will reduce the cost of production and increase the useful life of the well.
  • a method of making a proppant may include adding a dry ceramic precursor to a granuiator, adding a slurry to the granuiator, granulating the dry ceramic precursor and the slurry to form densified granules, and firing the densified granules to form a ceramic proppant.
  • the dry ceramic precursor may include an alumina- or aluminosilicate-containing material, such as, for example, at least one of kaolin, ball clay, bauxitic kaolin, smectite clay, bauxite, gibbsite, boehmite, metakaoSin, or diaspora.
  • an alumina- or aluminosilicate-containing material such as, for example, at least one of kaolin, ball clay, bauxitic kaolin, smectite clay, bauxite, gibbsite, boehmite, metakaoSin, or diaspora.
  • the slurry may include a recycled proppant material.
  • the recycled proppant materia! may include a fired recycled proppant material, a green recycled proppant material, or a combination thereof.
  • the recycled proppant material may include oversized particles and/or undersized particles.
  • FIG. 1 shows an exemplary proppant prepared by adding an exemplary slurry to a dry ceramic precursor.
  • FIG. 2 shows an exemplary proppant particle prepared by adding an exemplary slurry to a dry ceramic precursor.
  • a method of making a proppant may include adding a dry ceramic precursor to a granulator, adding a slurry to the granulator, granulating the dry ceramic precursor and the slurry to form densified granules, and firing the densified granules to form a ceramic proppant.
  • the dry ceramic precursor may include an alumina- or aluminosilicate-containing material.
  • the alumina- or aluminosilicate-containing material may include an alumina- or aluminosilicate-containing material.
  • aluminosilicate-containing material may include at least one of kaolin, ball clay, bauxitic kaolin, smectite clay, bauxite, gibbsste, boehmite, metakaoiin, or diaspora.
  • aluminosilicate-containing material other ceramic precursors may be used.
  • Kaolin is a common component in manufacturing for proppants for medium to deep hydraulic fracture treatments.
  • Kaolin is sometimes referred to as china clay or hydrous kaolin, and contains predominantly the mineral kaolinite, together with small concentrations of various other minerals.
  • Kaolinite may also be generally described as an aluminosilicate, a!uminosilicate clay, or hydrous aluminosilicate (e.g., AI 2 Si 2 0 5 (OH)4).
  • Kaolin clays were formed in geological times by the weathering of the feldspar component of granite.
  • Primary kaolin clays are those which are found in deposits at the site at which they were formed, such as those obtained from deposits in South West England, France, Germany, Spain, and the Czech Republic.
  • Sedimentary kaolin clays are those which were flushed out from the granite matrix at their formation site and were deposited in an area remote from their formation site, such as in a basin formed in the surrounding strata.
  • etakaolin is a form of calcined kaolin.
  • Calcined kaolins are kaolins that have been converted from the corresponding (naturally occurring) hydrous kaolin to the dehydroxy!ated form by thermal methods. Calcination changes at least some of the kaolin structure from crystalline to amorphous. The degree to which hydrous kaolin undergoes changes in crystalline form may depend on the amount of heat to which it is subjected. Initially, dehydroxylation of the hydrous kaolin occurs on exposure to heat. At temperatures below about 850-900 °C, the kaolin may be considered to be virtually dehydroxylated with the resultant amorphous structure commonly being referred to as being a metakaolin. Calcination in this temperature range may be referred to as partial calcination and the product may also be referred to as a partially calcined kaolin.
  • the furnace, kiln, or other heating apparatus used to effect calcining of the hydrous kaolin may be of any known kind. Calcination of the hydrous kaolin may take place, for example, in an oxidising atmosphere. A typical procedure may involve heating kaolin in a ki!n, for example, in a conventional rotary kiln. According to some embodiments, the kaolin may be introduced into the kiln as an extrudate from a mill, such as, a pug mill.
  • the kaolin may have a starting moisture content of about 25% by weight to facilitate the extrusion of the kaolin, and the extrudate may then form into pellets as a result of the calcination process.
  • a small amount of a binder may be added to the kaolin to provide "green strength" to the kaolin so as to prevent the kaolin from completely breaking down into powder form during the calcination process.
  • the temperature within a kiln used to create metakaolin should be within a specified range, typically above about 850° C but typically not greater than about 950 °C. At approximately 950 °C, amorphous regions of metakaolin begin to re- crystallize.
  • the period of time for calcination of kaolin to produce metakaolin is based upon the temperature in the kiln to which the kaolin is subjected. Generally, the higher the temperature, the shorter the calcination time, and conversely, the lower the temperature, the higher the calcination time.
  • the calcination process may include soak calcining in which the hydrous kaolin or clay is calcined for a period of time during which the chemistry of the material is gradually changed by the effect of heating.
  • the soak calcining may be for a period of, for example, at least 1 minute, at least 10 minutes, at least 30 minutes, at least 1 hour, or more than 5 hours.
  • Known devices suitable for carrying out soak calcining may include high temperature ovens, rotary kilns, and vertical kilns.
  • the calcination process may include flash calcining, in which the hydrous kaolin is typically rapidly heated over a period of less than one second, such as, for example, less than about 0.5 seconds.
  • Flash calcination refers to heating a material at an extremely fast rate, almost instantaneously.
  • the heating rate in a flash calciner may be of the order of about 56,000 °C per second or greater, such as about 100,000 °C per second, or about 200,000 °C per second.
  • metakaolin may be prepared by flash calcination, wherein the kaolin clay may be exposed to a temperature greater than about 500 °C for a time not more than about 5 seconds.
  • the clay may be calcined to a temperature in the range of from about 550 °C to about 1200 °C. According to some embodiments, the temperature may be as high as about 1500 °C for microsecond periods. According to some embodiments, the kaolin clay may be calcined to a temperature in the range of from about 800 °C to about 1 100 °C, such as, for example, from about 900 °C to about 1050 °C, or from about 950 °C to about 1000 °C. The clay may be calcined for a time less than about 5 seconds, such as, for example, less than 1 second, less than 0.5 seconds, less than about 0.2 seconds, or less than 0.1 second.
  • Flash calcination of kaolin particles gives rise to relatively rapid blistering of the particles caused by relatively rapid dehydroxylation of the kaolin.
  • Water vapor is generated during calcination which may expand extremely rapidly, generally faster than the water vapor can diffuse through the crystal structure of the particles.
  • the pressures generated are sufficient to produce sealed voids as the interlayer hydroxy! groups are driven off, and it is the swollen interlayer spaces, voids, or blisters between the kaolin platelets which typify flash calcined kaolins.
  • the method may be performed without adding water to the granulator separate from the slurry. It is believed that in some embodiments, the slurry may provide sufficient water to create a composition sufficient for granulation. This may improve the overall flow and efficiency of a proppant-making process. According to some embodiments, the method may include adding water to the granulator prior to granulating the dry ceramic powder and the slurry.
  • the granulator may be any type of granulation device, such as, for example, an Eirich mixer, a pan peilefizer, or a pin mill.
  • the slurry may include a recycled proppant material.
  • the term "recycled proppant material” refers to proppant material that was segregated or set aside from a previous manufacturing process.
  • the recycled proppant material may include a fired (e.g., sintered or calcined) recycled proppant material.
  • fired recycled proppant material include, but are not limited to, proppant particles that were fired from green bodies and screened after the firing process.
  • Fired recycled proppant materials may include, for example, undersized fired particles and/or oversized fired particles formed during calcination or firing of the green proppants.
  • the fired recycled proppant material may include fines from particles that were crushed or ground during processing.
  • the recycled proppant material may include a green recycled proppant material.
  • a green recycled proppant material may include, for example, green (e.g. , unfired or unsintered) proppant particles such as those from a granulator, thai have been screened or milled. Examples of green recycled proppant particles may include undersized granules or oversized granules that were segregated during manufacturing.
  • the recycled proppant material may include oversized ceramic particles, undersized ceramic particles, or both.
  • the recycled proppant material may include a milled recycled proppant material, such as, for example, fired or green particle that has been milled to provide a desired size distribution.
  • the recycled proppant material may have been optionally screened to narrow its particle size distribution.
  • the resulting slurry may have a multimodal particle size distribution, such as, for example, a bimodal particle size distribution resulting from one mode corresponding to the undersized particles and one mode corresponding to the oversized particles.
  • the use of a recycled proppant material may improve the densification of proppant particles.
  • the undersized particles may fill interstitial voids between the oversized particles, resulting in a greater packing density, which may increase the bulk density or apparent density of the finished proppants.
  • the slurry may include a solids component of the slurry is a different material from the dry ceramic precursor material.
  • the dry ceramic precursor material may include an unfired clay material, such as kaolin, and the slurry may include a fired version of the same material, such as, for example, sintered or calcined kaolin.
  • the dry ceramic precursor may include kaolin and the slurry may include metakaolin.
  • the dry ceramic precursor may include a metakaolin and the slurry may include a fired proppant material, such as, for example, undersized or oversized proppanfs from a screening operation or fines from proppant processing.
  • the dry ceramic precursor may include a ceramic precursor, such as, for example, powdered alumina, and the slurry may include a hydrous material, such as kaolin or green granules.
  • the slurry may have a solids content ranging from about 10 wt% to about 80 wt% of the slurry, such as, for example, ranging from about 10 wt% to about 50 wt%, ranging from about 50 wt% to about 80 wt%, ranging from about 30 wt% to about 70 wt%, ranging from about 35 wt% to about 85 wt%, ranging from about 10 wt% to about 30 wt%, ranging from about 20 wt% to about 40 wt%, ranging from about 40 wt% to about 60 wt%, ranging from about 30 wt% to about 40 wt%, ranging from about 35 wt% to about 45 wt%, ranging from about 40 wt% to about 50 wt%, ranging from about 45 wt% to about 55 wt%, ranging from about 50 wt% to about 60 wt%, ranging
  • the dry ceramic precursor may include a binder.
  • the slurry may include a binder.
  • the slurry may include a binder, for example, when the insoluble material is a green or unfired composition that contains a binder, or a binder may be separately added to the slurry apart from the insoluble material.
  • binders or binding agents may include, for example, methyl cellulose, polyvinyl butyrals, emulsified acrylates, polyvinyl alcohols, polyvinyl pyrroiidones, polyacrylics, starch, silicon binders, polyacrylates, silicates, polyethylene imine, lignosuiphonates, phosphates, alginates, and
  • Some possible solvents may include, for example, water, alcohols, ketones, aromatic compounds, and hydrocarbons.
  • the strength of a proppant may be indicated from a proppant crush resistance test described in ISO 13503-2: "Measurement of Properties of Proppants Used in Hydraulic Fracturing and Gravel-packing Operations.”
  • a sample of proppant is first sieved to remove any fines (i.e., undersized pellets or fragments that may be present), then placed in a crush cell where a piston is then used to apply a confined closure stress of some magnitude above the failure point of some fraction of the proppant pellets.
  • the sample is then re-sieved and the weight percent of fines generated as a result of pellet failure is reported as percent crush.
  • the ceramsc proppant may have an ISO crush resistance of less than or equal to about 10% fines at 10,000 psi, such as, for example, less than or equal to about 9.5% fines, less than or equal to about 9.0% fines, less than or equal to about 8.8% fines, less than or equal to about 8.6% fines, less than or equal to about 8.5% fines, less than or equal to about 8.3% fines, less than or equal to about 8.2% fines, less than or equal to about 8.1 % fines, or less than or equal to about 8.0% fines, less than or equal to about 7.5% fines, less than or equal to about 7% fines, less than or equal to about 8.5% fines, less than or equal to about 6% fines, or less than or equal to about 5.5% fines at 10,000 psi.
  • the ceramic proppant may have a sphericity greater than or equal to about 0.6, such as, for example, greater than or equal to about 0.85, greater than or equal to about 0.7, greater than or equal to about 0.75, greater than or equal to about 0.8, greater than or equal to about 0.85, greater than or equal to about 0.9, greater than or equal to about 0.91 , greater than or equal to about 0.92, greater than or equal to about 0.93, greater than or equal to about 0.94, or greater than or equal to about 0.95.
  • 0.6 such as, for example, greater than or equal to about 0.85, greater than or equal to about 0.7, greater than or equal to about 0.75, greater than or equal to about 0.8, greater than or equal to about 0.85, greater than or equal to about 0.9, greater than or equal to about 0.91 , greater than or equal to about 0.92, greater than or equal to about 0.93, greater than or equal to about 0.94, or greater than or equal to about 0.95.
  • the ceramic proppant may have a roundness greater than or equal to about 0.6, such as, for example, greater than or equal to about 0.91 , greater than or equal to about 0.92, greater than or equal to about 0.93, greater than or equal to about 0.94, or greater than or equal to about 0.95.
  • the ceramic proppant may have an apparent specific gravity greater than or equal to about 1.50, greater than or equal to about 1.60, greater than or equal to about 1 .70, greater than or equal to about 1.80, greater than or equal to about 1.90, greater than or equal to about 2,0, greater than or equal to about 2.10, greater than or equal to about 2.20, greater than or equal to about 2.30, greater than or equal to about 2.40, greater than or equal to about 2.50, greater than or equal to about 2.80. greater than or equal to about 2.70, greater than or equal to about 2.71 , greater than or equal to about 2.72, greater than or equal to about 2.73. greater than or equal to about 2.74, greater than or equal to about 2,75, greater than or equal to about 2.76, or greater than or equal to about 2.77.
  • the ceramic proppant may have a density ranging from about 1.50 g/cc to about 2.90 g/cc.
  • the ceramic proppant may have an average apparent density ranging from about 1.50 g/cc to about 2,0 g/cc, ranging from about 1.80 g/cc to about 2.80 g/cc, ranging from about 2.0 g/cc to about 2.90 g/cc, ranging from about 2.40 g/cc to about 2.9 g/cc, ranging from about 2.50 g/cc to about 2.85 g/cc, ranging from about 2,8 g/cc to about 2.85 g/cc, ranging from about 2.75 g/cc to about 2.85 g/cc, ranging from about 2,70 g/cc to about 2.80 g/cc, ranging from about 2.71 g/cc to about 2.77 g/cc, ranging from about 2.71 g/cc to
  • the ceramic proppant may have bulk density greater than or equal to about 1 ,54 g/cc,
  • the ceramic proppant may have a bulk density greater than about 1.55 g/cc, greater than about 1.56 g/cc, greater than about 1.57 g/cc, or greater than about 1.58 g/cc.
  • the slurry may include a solids content in which greater than or equal to about 60% by weight of the particles have a particle size greater than or equal to about 600 pm (30 mesh) and less than or equal to about 1200 pm (18 mesh), such as, for example, greater than or equal to about 85% by weight of the particles have a particle size greater than or equal to about 600 pm (30 mesh) and less than or equal to about 1200 pm (16 mesh).
  • the slurry may include a solids content in which greater than or equal to about 30% by weight of the particles have a particle size greater than or equal to about 400 pm (40 mesh) and less than or equal to about 840 pm (20 mesh), such as, for example, in which greater than or equal to about 35% by weight of the particles have a particle size greater than or equal to about 400 m (40 mesh) and less than or equal to about 840 pm (20 mesh),
  • the slurry may include a solids content in which greater than or equal to about 30% by weight of the particles have a particle size greater than or equal to about 400 pm (40 mesh) and less than or equal to about 840 pm (20 mesh), such as, for example, in which greater than or equal to about 35% by weight of the particles have a particle size greater than or equal to about 400 pm (40 mesh) and less than or equal to about 840 pm (20 mesh).
  • the slurry may include a solids content in which greater than or equal to about 90% by weight of particles having a particle size greater than or equal to about 150 pm (100 mesh), such as, for example, in whichgreater than or equal to about 95% by weight, greater than or equal to about 96% by weight, greater than or equal to about 97% by weight, greater than or equal to about 98% by weight, or greater than or equal to about 99% by weight having a particle size greater than or equal to about 150 pm (100 mesh).
  • the slurry may include a solids content in which greater than or equal to about 90% by weight of particles having a particle size less than or equal to about 100 (140 mesh), such as, for example, in which greater than or equal to about 95% by weight, greater than or equal to about 96% by weight, greater than or equal to about 97% by weight, greater than or equal to about 98% by weight, or greater than or equal to about 99% by weight having a particle size less than or equal to about 100 ⁇ (140 mesh),
  • the dry ceramic precursor may be sized using various milling or grinding techniques, including, for example, attrition grinding and autogenous grinding (i.e., grinding without a grinding medium), and may be ground either by a dry grinding or a wet grinding process.
  • attrition grinding and autogenous grinding i.e., grinding without a grinding medium
  • the resulting material may be dried before it is mixed with the slurry.
  • the grinding may be accomplished by a single grinding step or may involve more than one grinding step.
  • a jet mill may be used to prepare a first batch of particles having a first particle size distribution.
  • the particles are introduced into a stream of fluid, generally air, which circulates the particles and induces collisions between the particles.
  • the forces in the jet mill can alter the particle size distribution of the particles to achieve a desired distribution.
  • the exact configuration will vary based on the properties of the feed material and the desired output properties.
  • the appropriate configuration for a given application can be readily determined by those skilled in the art.
  • the dry ceramic precursor or solids component of the slurry may have a multimodal distribution of particles.
  • a multimodal distribution may be created by jet milling more than one batch of particles and mixing the particles together.
  • a multimodal distribution may optionally be sized in a ball mill. Similar to jet milling multiple batches to different particle sizes and mixing them, ball milling may result in a multimodal particle size distribution, which can improve the compacity of the powder. In contrast to a jet milling process, however, acceptable results may be achieved in a single ball-milled batch of particles (i.e., there is no requirement to prepare multiple batches and mix them).
  • batches with two different particle size distributions can be simultaneously milled in the bail mill, resulting in a powder with a multimodal particle size distribution.
  • a ball mill contains a chamber in which the ceramic precursor and a collection of balls collide with each other to alter the precursor material's particle size.
  • the chamber and balls are typically made of metal, such as aluminum or steel.
  • the appropriate configuration for the bail mil! e.g., the size and weight of the metal balls, the milling time, the rotation speed, etc.
  • the ball milling process can be either a batch process or a continuous process.
  • Various additives may also be used to increase the yields or efficiency of the milling.
  • the additives may act as surface tension modifiers, which may increase the dispersion of fine particles and reduce the chance that the particles adhere to the walls and ball media.
  • Suitable additives are known to those skilled in the art and include aqueous solutions of modified hydroxylated amines and cement admixtures, in some embodiments, the ball mill may be configured with an air classifier to reintroduce coarser particles back into the mill for a more accurate and controlled milling process.
  • a slurry in place of water, or in addition to water, during granulation may increase the solids content of the granulated composition.
  • packing density may be improved, resulting in denser and/or mechanically stronger proppants after firing (e.g., heating or sintering).
  • the slurry composition includes a recycled proppant material, whether a green recycled proppant material, a fired recycled proppant material, combination thereof, or any other form of recycled proppant material
  • a slurry may allow for the addition of a greater weight percent of proppant precursor (either in green form or in fired form, such as, for example, sintered or calcined form) to be included in the granulation mixture.
  • the use of a slurry may also allow for certain types of particles, such as green or fired oversized or undersized particles, to be re-incorporated into the granulation process, thereby improving the utility of these particles and the overall efficient use of the materials.
  • the proppants described in this disclosure may be used by themselves to create a proppant pack. According to some embodiments, the proppants described in this disclosure may be used in conjunction with other proppant particles as part of a proppant pack.
  • a slurry of 50 wt% metakaolin was prepared by placing 1000 grams of water in a beaker, adding 1000 grams of metakaolin, and mixing to create the slurry.
  • a typical chemical composition for the metakaolin is shown below in Table 1.
  • the H of the slurry was adjusted to pH 9 by adding sodium hydroxide.
  • the viscosity of the slurry was measured using a Brookfie!d viscometer and was 295 cps.
  • Control A control proppant (“Control") was prepared by placing 3000 grams of the metakaolin in an Eirich mixer. 1000 grams of water with 15 grams of PVA was added to the metakaolin and mixed at 60 rpm for 5 minutes to prepare granulations.
  • a first proppant sample (sample A) was prepared by placing 2000 g of dry metakaolin in an Eirich mixer. 1575.7 grams of the 50 wt% slurry was added to the metakaolin. The resulting slurry-metakaolin composition was mixed at 80 rpm for 5 minutes. After adding the slurry, 185 grams of water and 15 grams of PVA were added to the mixture. The resulting composition was mixed at 60 rpm for 5 minutes to prepare granulations. The total moisture content of the granulated sample A was about 28 wt% based on the total metakaolin content of 2787.9 grams and the total water content of about 972.9 grams.
  • a second proppant sample (sample B) was prepared by placing 3000 grams of dry metakaolin in an Eirich mixer. 2412.8 grams of the 50 wt% slurry was added to the metakaolin. The slurry-metakaolin composition was mixed at 60 rpm for 5 minutes. After adding the slurry, 357 grams of water and 15 grams of PVA. The resulting composition was mixed at 80 rpm for 5 minutes to prepare granulations. The total moisture content of granulated sample B was determined to be about 28 wt% based on the total metakaolin content of 4206.3 grams and the total water content of about 1563.3 grams.
  • sample C A third proppant sample (sample C) was prepared in the same way as sample B, except that the water and 30 grams of PVA was added to the 50 wt% slurry prior to mixing the slurry with the dry metakaolin. Thus, for sample C only one addition of moisture was added to the dry metakaolin. The resulting mixture was mixed at 60 rpm for 5 minutes to prepare granulations. The total moisture content of sample C was about 26 wt%, as in sample B.
  • the crush strength of samples A ⁇ C appears to be comparable to or even greater than the control sample.
  • the crush strength for all of the samples A- C and the control were relatively similar, with sample C being slightly higher than samples A and B and the control.
  • a proppant prepared using a slurry instead of, or in addition to, water when preparing the granulations may also improve densificatson of the proppants (e.g., they may have a higher specific gravity and density).
  • the examples also show that a binder can be incorporated into the slurry prior to adding the slurry to the dry powder, as in sample C, while still achieving comparable or improved properties.
  • a slurry instead of only water adds extra mineral to the resulting mixture, thereby increasing the bulk density.
  • the slurry may also improve the packing of the inorganic materials during granulation when compared to the dry powder and water. This improved packing may result in a denser granulation bead and a denser proppant after firing.
  • was surprisingly found that using a slurry instead of, or in addition to, water when preparing the granulations substantially improved the output of each granulation. Based on this finding, the use of a slurry may also improve the yield of various proppant preparation methods,
  • a sample proppant prepared with fine particles was prepared using fine metakaolin particles by placing 2403 grams of the fine particles in an Eirich mixer and adding 756 grams of water. The resulting composition was mixed for 5 minutes at 32 rpm. The resulting granules had a moisture content of 23,2 wt%. The granules were then fired at 1500 °C for 3 hours ' .
  • Three additional proppant samples, D-F were prepared by mixing green screen oversized pellets and undersised pellets into three separate slurries with water comprising 38.2 wt% (sample D), 50.0 wt% (sample E), and 55,0 wt% (sample F) of the slurries.
  • the oversized pellets and undersized pellets were mixed into the slurries without pre-screening before being made into a slurry.
  • the chemical composition of the slurries was determined by x-ray fluorescence (XRF) and is shown below in Table 3.
  • sample D 38.2 wt% slurry
  • 2403 grams of fines were added to an Eirich mixer.
  • 1420 grams of the 38.2 wt% slurry with PVA was added to the dry fines and mixed for 5 minutes at 32 rpm to granulate the sample.
  • the moisture content of the resulting granules was 22.1 wt%.
  • Samples E and F were prepared in the same way as sample D, except that 50.0 wt% and 55.0 wt% slurries were used, respectively.
  • the moisture contents of the granules prepared for samples E and F were 22.6 wt% and 21.4 wt%, respectively.
  • green oversized and undersized pellets can be used to form a slurry that may be added the dry proppant precursor powder to form a granulation composition.
  • the use of a slurry in place of water appears to result in good quality proppants having an ISO crush resistance of less than 9 wt% fines.
  • samples D and E have about 8 wt% fines at 10,000 psi.
  • Sample F resulted in only 5.5 wt% fines at 10,000 psi.
  • F!G. 2 shows a proppant of sample D, showing the low interna! porosity of the proppant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Un procédé de fabrication d'un agent de soutènement peut consister à ajouter un précurseur à base de céramique sèche dans un granulateur, ajouter une boue dans le granulateur, granuler le précurseur à base de céramique sèche et la boue afin de former des granules densifiées, et cuire les granules densifiées pour former un agent de soutènement céramique. Le précurseur à base de céramique sèche peut comprendre un matériau contenant une alumine ou un aluminosilicate, comme par exemple au moins un matériau parmi kaolin, ball clay, kaolin bauxitique, argile de type smectite, bauxite, gibbsite, boehmite, métakaolin ou diaspora. La boue peut comprendre un matériau de soutènement recyclé, tel que qu'un matériau de soutènement recyclé cuit ou un matériau de soutènement recyclé vert.
PCT/US2015/050855 2014-09-19 2015-09-18 Addition de boue contenant des minéraux pour la formation d'un agent de soutènement Ceased WO2016044688A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/512,087 US20170275209A1 (en) 2014-09-19 2015-09-18 Addition of mineral-containing slurry for proppant formation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462052541P 2014-09-19 2014-09-19
US62/052,541 2014-09-19

Publications (1)

Publication Number Publication Date
WO2016044688A1 true WO2016044688A1 (fr) 2016-03-24

Family

ID=55533891

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2015/050855 Ceased WO2016044688A1 (fr) 2014-09-19 2015-09-18 Addition de boue contenant des minéraux pour la formation d'un agent de soutènement

Country Status (2)

Country Link
US (1) US20170275209A1 (fr)
WO (1) WO2016044688A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018063212A1 (fr) * 2016-09-29 2018-04-05 Halliburton Energy Services, Inc. Broyage de matières particulaires de champ pétrolifère
WO2018077799A1 (fr) * 2016-10-31 2018-05-03 Imerys Technology Center Austria Gmbh Granules de toiture réfractaires frittés
CN110898860A (zh) * 2018-09-14 2020-03-24 萍乡市华填化工填料有限公司 改进型网孔支撑剂及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11578260B2 (en) 2017-12-13 2023-02-14 U.S. Ceramics LLC Proppants and methods of making and use thereof
CN108913927B (zh) * 2018-08-02 2020-06-16 株洲佳邦难熔金属股份有限公司 热沉用钼铜合金的原料混合方法、制备工艺及产品

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713203A (en) * 1985-05-23 1987-12-15 Comalco Aluminium Limited Bauxite proppant
US20080058228A1 (en) * 2006-08-30 2008-03-06 Carbo Ceramics Inc. Low bulk density proppant and methods for producing the same
US20090038797A1 (en) * 2007-07-18 2009-02-12 Oxane Materials, Inc. Proppants With Carbide and/or Nitride Phases
US20100105579A1 (en) * 2006-12-27 2010-04-29 Elena Mikhailovna Pershikova Proppant, proppant production method and use of proppant
US20100113251A1 (en) * 2008-10-31 2010-05-06 Laurie San-Miguel High strength proppants
US20110111990A1 (en) * 2008-04-28 2011-05-12 Elena Mikhailovna Pershikova Strong low density ceramics

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH490110A (de) * 1969-02-28 1970-05-15 Spemag Ag Mischmaschine
US8614157B2 (en) * 2011-03-25 2013-12-24 Carbo Ceramics, Inc. Sintered particles and methods for producing sintered particles from a slurry of an alumina-containing raw material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713203A (en) * 1985-05-23 1987-12-15 Comalco Aluminium Limited Bauxite proppant
US20080058228A1 (en) * 2006-08-30 2008-03-06 Carbo Ceramics Inc. Low bulk density proppant and methods for producing the same
US20100105579A1 (en) * 2006-12-27 2010-04-29 Elena Mikhailovna Pershikova Proppant, proppant production method and use of proppant
US20090038797A1 (en) * 2007-07-18 2009-02-12 Oxane Materials, Inc. Proppants With Carbide and/or Nitride Phases
US20110111990A1 (en) * 2008-04-28 2011-05-12 Elena Mikhailovna Pershikova Strong low density ceramics
US20100113251A1 (en) * 2008-10-31 2010-05-06 Laurie San-Miguel High strength proppants

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018063212A1 (fr) * 2016-09-29 2018-04-05 Halliburton Energy Services, Inc. Broyage de matières particulaires de champ pétrolifère
GB2567383A (en) * 2016-09-29 2019-04-10 Halliburton Energy Services Inc Milling oilfield particulates
US11285489B2 (en) 2016-09-29 2022-03-29 Halliburton Energy Services, Inc. Milling oilfield particulates
GB2567383B (en) * 2016-09-29 2022-04-20 Halliburton Energy Services Inc Milling oilfield particulates
WO2018077799A1 (fr) * 2016-10-31 2018-05-03 Imerys Technology Center Austria Gmbh Granules de toiture réfractaires frittés
CN110898860A (zh) * 2018-09-14 2020-03-24 萍乡市华填化工填料有限公司 改进型网孔支撑剂及其制备方法
CN110898860B (zh) * 2018-09-14 2023-06-06 萍乡市华填化工填料有限公司 改进型网孔支撑剂及其制备方法

Also Published As

Publication number Publication date
US20170275209A1 (en) 2017-09-28

Similar Documents

Publication Publication Date Title
RU2346971C2 (ru) Проппант, способ его получения и способ его применения
EP2197976B1 (fr) Agents de soutènement et additifs anti-reflux obtenus à partir de minéraux de sillimanite, leurs procédés de fabrication et d'utilisation
US7648934B2 (en) Precursor compositions for ceramic products
CA2905709C (fr) Agent de soutenement leger a resistance amelioree et ses procedes de fabrication
US7678723B2 (en) Sintered spherical pellets
CA2466399C (fr) Materiau de soutenement en silice mixte
CA2875500C (fr) Agents de soutenement et additifs antireflux comprenant de l'argile de calcination eclair, procedes de fabrication et procedes d'utilisation
CA2608857A1 (fr) Granules spheriques frittes utiles pour un agent de soutenement de puits de gaz et de petrole
US20090227480A1 (en) Angular abrasive proppant, process for the preparation thereof and process for hydraulic fracturing of oil and gas wells
US20170275209A1 (en) Addition of mineral-containing slurry for proppant formation
US20160053162A1 (en) Method of manufacturing of light ceramic proppants and light ceramic proppants
CN102753501A (zh) 陶瓷颗粒以及其制造方法
US20170226410A1 (en) Proppant Material Incorporating Fly Ash and Method of Manufacture
US20180258343A1 (en) Proppants having fine, narrow particle size distribution and related methods
RU2650149C1 (ru) Шихта для изготовления легковесного кремнезёмистого проппанта и проппант
AU2002340238A1 (en) Composite silica oxide proppant material

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15841935

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15841935

Country of ref document: EP

Kind code of ref document: A1